EP0273101B1 - Procédé de préparation de 3-(alkylthio)-aldehydes - Google Patents

Procédé de préparation de 3-(alkylthio)-aldehydes Download PDF

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Publication number
EP0273101B1
EP0273101B1 EP87110780A EP87110780A EP0273101B1 EP 0273101 B1 EP0273101 B1 EP 0273101B1 EP 87110780 A EP87110780 A EP 87110780A EP 87110780 A EP87110780 A EP 87110780A EP 0273101 B1 EP0273101 B1 EP 0273101B1
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EP
European Patent Office
Prior art keywords
alkylthio
exchange resin
catalyst
aldehydes
unsaturated aliphatic
Prior art date
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Expired - Lifetime
Application number
EP87110780A
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German (de)
English (en)
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EP0273101A1 (fr
Inventor
Stanley R. Sandler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema Inc
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Atochem North America Inc
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups

Definitions

  • This invention relates to the facile preparation of 3-alkylthio)aldehydes by the reaction of a C1-C12 alkyl mercaptan with a C3-C10 unsaturated aliphatic aldehyde in the presence of a specified exchange resin catalyst. More particularly, this invention relates to the preparation of 3-(C1-C12 alkylthio) C3-C10 alkanals in the presence of a catalytic amount of weakly basic and exchange resin having polyamine functionally and being in the free base form.
  • the products of the process of this invention have various uses including, for example, intermediates for the preparation of pesticides and antioxidants and as odorant or flavouring agents.
  • Triethylamine and other basic catalysts have also been reported as used for the reaction of lower alkyl mercaptans with ⁇ , ⁇ -unsaturated aliphatic aldehydes2.
  • the prior art catalyst containing the hydroxide functionally suffers from the disadvantage of producing high boiling or polymeric product.
  • Hall et al.2 agree with this conclusion and state on line 6 of their paper "The physical constants (b.p.
  • the catalysts of the present invention have the advantage of being reusable and that the product does not contain any significant amounts of high boiling components or non-volatiles.
  • the present invention is a process for the preparation of 3-(alkylthio)aldehydes by the reaction at a temperature within the range of about 0 to about 100°C of a C1-C12 alkyl mercaptan with a C3-C10 ⁇ , ⁇ -unsaturated aliphatic aldehyde in the presence of a weakly basic exchange resin having polyamine functionality and being in the free base form.
  • the process of this invention represents an unexpected improvement in the preparation of 3-(C1-C12 alkylthio)C3-C10 aldehydes. More preferably, it involves the preparation of 3-(C1-C6 alkylthio)C3-C6 alkanals from the corresponding alkyl mercaptans and a, ⁇ -unsaturated aldehydes.
  • the alkyl groups of the mercaptans of the process includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomeric forms thereof.
  • alkyl groups include cycloalkyls including, for example, cyclopentyl, cyclohexyl, cycloheptyl, cycloctyl and the like.
  • the C3-C10 aliphatic aldehydes are ⁇ , ⁇ -unsaturated aldehydes and include, for example, acrolein, crotonaldehyde, pentenal, hexanal, heptenal, 2-methyl-2-pentenal, octenal, 2-methyl-2-hexenal, nonenal, and decenal.
  • the preferred mercaptans are the C1-C3 alkyl mercaptans and the preferred aldehydes are the C3-C6 ⁇ , ⁇ -unsaturated aldehydes.
  • the temperature at which the reaction is carried out ranges from about 0 to about 100°C, preferably from about 25 to 100°C and more preferably from about 50 to 80°C.
  • the pressure ranges from 1.01 to 50.66 Bar (1 to 50 atmospheres) and preferably from 1.01 to 20.27 Bar ( 1 to 20 atmospheres).
  • the process may be carried out in the liquid phase or in the vapor phase depending on the temperature and/or pressure employed.
  • the ratio of the reactants in the process reaction generally ranges from about 1: 1 to about 1: 3 and is preferably at about 1: 1 to about 1: 1.5 moles of alkyl mercaptan per mole of unsaturated aldehyde.
  • a solvent is optional for the reaction but may be employed, particularly when the reaction is carried out with higher alkyl compounds.
  • Suitable solvents are, for example, tetrahydrofuran, dioxane and water.
  • the critical feature of the present invention is in the use as a catalyst of a weakly basic ion exchange resin having polyamine functionality and being in the free base form.
  • the matrix resin for the catalyst material can be, for example, methacrylic/divinylbenzene, acrylic/divinylbenzene, styrene/divinylbenzene, styrene/divinylbenzene/acrylic and the like, such resins being crosslinked to various degrees through crosslinking agents or copolymer components (eg. divinylbenzene) which have substituent groups which react with one-another across the polymer chains.
  • the preferred matrix resins are those which provide microporous or macroreticular structures and are in bead form.
  • the preferred macroreticular catalysts comprise resin matrixes wherein the polyamine functionality has pendant tertiary amine groups.
  • An example of this type of preferred catalyst which can be obtained from Rohm & Haas Company, is the product designated Amberlyst® A21.
  • Other such catalysts for this invention which are commercially available are the Rohm & Haas Company products designated Amberlite® IRA35, IRA45, IRA47S, IRA60, IRA68, and IRA93.
  • the resin catalyst is used in varying amounts in the process depending upon the mode of operation.
  • the catalyst is preferably stirred with the reactants using 1 to 50 grams of catalyst per mole of either reactant.
  • a preferred range is 1 to 20 grams per mole of either reactant.
  • a catalyst bed is used in which the reactants, either in liquid or vapor phase, are passed over the catalyst preferably at a molar velocity ranging between about 100 to about 4000 gram-moles or mercaptan per kilogram of catalyst per 24 hours.
  • the catalyst bed may be of various lengths with sufficient catalyst exposure to give high conversion rates per pass.
  • the unreacted compounds are removed and recycled with sufficient make-up reactants to provide the appropriate ratio of mercaptan to aldehyde.
  • Unused Amberlyst® A-21 catalyst is first washed with distilled water and methanol solution as described below before being used to prepare 3-(ethylthio)butanal. 178.0 g of the catalyst is washed successively twice at room temperature with each of 200 g water, 200 g 33% aqueous methanol (by volume), and 200 g methanol. Then the catalyst was dried under reduced pressure at 50°C to constant weight.
  • Crotonaldehyde and ethyl mercaptan are fed into a catalytic bed of Amberlyst® A-21 which was kept at 50°C at such a rate to keep the mole ratio of each approximately 1: 1.
  • the unreacted materials are recovered and recycled and the product 3-(ethylthio)butanal is obtained as a stripped crude or a distilled product.
  • Crotonaldehyde, nitrogen and ethyl mercaptan are brought together in an adequate mixing device and thoroughly mixed prior to being fed into a packed-bed containing a mixture of Amberlyst® A-21 and glass beads which are kept at a temperature above 50°C.
  • the crotonaldehyde and ethyl mercaptan feed rates were controlled by rotometers to keep the mole ratio at about 1: 1.
  • the product stream was monitored by gas chromatography. The liquid product is separated from the unreacted starting materials which are recovered for reuse.
  • the catalysts of this invention provide superior results for the process of preparing 3-(alkylthio)aldehydes from mercaptans and unsaturated aldehydes since they provide products with low non-volatile content.
  • the prior art process of preparing the alkylthioaldehydes, eg. 3-(ethylthio)propanal, utilizing the anion exchange resin in the hydroxide form (Amberlite® IRA 400) is not suitable for preparing, for example, 3-(ethylthio)butanal, since the product will have a high non-volatile content (or polymers).
  • the catalysts of this invention are reusable and non-contaminating to the product because they can be easily separated by simple filtration or decantation. They can also be packed in columns which make these resin catalysts suitable for continuous operation. Triethylamine, on the other hand, is difficult to remove from the product causing a decrease in storage stability.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (12)

1. Procédé de préparation de 3-(alkylthio en C₁ à C12)-(aldéhydes en C₃ à C10), qui consiste à faire réagir à une température comprise dans la plage d'environ 0 à environ 100°C un alkylmercaptan en C₁ à C12 avec un aldéhyde aliphatique à non-saturation α, β en C₃ à C10 en présence d'une quantité catalytique d'une résine échangeuse faiblement basique présentant une fonctionnalité de polyamine et étant sous la forme base libre.
2. Procédé suivant la revendication 1, dans lequel la plage de températures va d'environ 25 à 100°C.
3. Procédé suivant la revendication 1, dans lequel l'alkylmercaptan est un alkylmercaptan en C₁ à C₆.
4. Procédé suivant la revendication 1, dans lequel l'aldéhyde aliphatique non saturé est un alcénal en C₃ à C₆.
5. Procédé suivant la revendication 1, dans lequel le 3-(alkylthio)aldéhyde produit est le 3-(éthylthio)butanal.
6. Procédé suivant la revendication 3, dans lequel l'aldéhyde aliphatique non saturé est un alcénal en C₃ à C₆.
7. Procédé suivant la revendication 1, dans lequel la fonctionnalité de polyamine de la résine échangeuse comprend des groupes amino tertiaires latéraux.
8. Procédé suivant la revendication 6, dans lequel la fonctionnalité de polyamine de la résine échangeuse comprend des groupes amino tertiaires latéraux.
9. Procédé suivant la revendication 8, dans lequel la résine échangeuse est macroréticulaire.
10. Procédé suivant la revendication 9, mis en oeuvre en phase vapeur.
11. Procédé suivant la revendication 9, mis en oeuvre en phase liquide.
12. Procédé suivant la revendication 9, dans lequel l'alkylmercaptan est l'éthylmercaptan et l'aldéhyde aliphatique non saturé est le crotonaldéhyde.
EP87110780A 1986-10-28 1987-07-24 Procédé de préparation de 3-(alkylthio)-aldehydes Expired - Lifetime EP0273101B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US92407786A 1986-10-28 1986-10-28
US924077 1986-10-28

Publications (2)

Publication Number Publication Date
EP0273101A1 EP0273101A1 (fr) 1988-07-06
EP0273101B1 true EP0273101B1 (fr) 1991-01-30

Family

ID=25449676

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EP87110780A Expired - Lifetime EP0273101B1 (fr) 1986-10-28 1987-07-24 Procédé de préparation de 3-(alkylthio)-aldehydes

Country Status (10)

Country Link
EP (1) EP0273101B1 (fr)
JP (1) JPS63112556A (fr)
AU (1) AU598842B2 (fr)
BR (1) BR8705579A (fr)
CA (1) CA1297908C (fr)
DE (1) DE3767858D1 (fr)
DK (1) DK561387A (fr)
ES (1) ES2020535B3 (fr)
IN (1) IN166197B (fr)
MX (1) MX168758B (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4944853A (en) * 1989-09-11 1990-07-31 Pennwalt Corporation Photochemical preparation of 3-(organothio) aldehydes

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3529940A (en) * 1966-04-25 1970-09-22 Sumitomo Chemical Co Apparatus for two-stage production of beta-methylmercaptopropionaldehyde
IT1037036B (it) * 1971-01-26 1979-11-10 Givaudan & Cie Sa Beta alchiltio aldeidi
DE2320544C2 (de) * 1973-04-21 1975-06-05 Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt Verfahren zur Herstellung von 3-Methylmercaptopropionaldehyd
FR2314917A1 (fr) * 1975-06-20 1977-01-14 Rhone Poulenc Ind Procede de fabrication de l'aldehyde beta-methylthiopropionique
DE10206490C1 (de) * 2002-02-16 2003-09-25 Wash Tec Holding Gmbh Vorrichtung zum Behandeln der Oberfläche von Fahrzeugen

Also Published As

Publication number Publication date
IN166197B (fr) 1990-03-24
BR8705579A (pt) 1988-05-24
DE3767858D1 (de) 1991-03-07
CA1297908C (fr) 1992-03-24
ES2020535B3 (es) 1991-08-16
AU7673387A (en) 1988-05-05
JPS63112556A (ja) 1988-05-17
AU598842B2 (en) 1990-07-05
DK561387A (da) 1988-04-29
DK561387D0 (da) 1987-10-27
EP0273101A1 (fr) 1988-07-06
MX168758B (es) 1993-06-07

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